US8479833B2 - Integrated enhanced oil recovery process - Google Patents
Integrated enhanced oil recovery process Download PDFInfo
- Publication number
- US8479833B2 US8479833B2 US12/906,547 US90654710A US8479833B2 US 8479833 B2 US8479833 B2 US 8479833B2 US 90654710 A US90654710 A US 90654710A US 8479833 B2 US8479833 B2 US 8479833B2
- Authority
- US
- United States
- Prior art keywords
- stream
- acid gas
- hydrocarbon
- gas
- absorber
- Prior art date
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Images
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/164—Injecting CO2 or carbonated water
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/34—Arrangements for separating materials produced by the well
- E21B43/40—Separation associated with re-injection of separated materials
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
- F25J3/0223—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0233—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 1 carbon atom or more
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0252—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of hydrogen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0266—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of carbon dioxide
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/50—Processes or apparatus using other separation and/or other processing means using absorption, i.e. with selective solvents or lean oil, heavier CnHm and including generally a regeneration step for the solvent or lean oil
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
- F25J2230/30—Compression of the feed stream
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
- F25J2230/80—Processes or apparatus involving steps for increasing the pressure of gaseous process streams the fluid being carbon dioxide
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
- F25J2260/80—Integration in an installation using carbon dioxide, e.g. for EOR, sequestration, refrigeration etc.
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P90/00—Enabling technologies with a potential contribution to greenhouse gas [GHG] emissions mitigation
- Y02P90/70—Combining sequestration of CO2 and exploitation of hydrocarbons by injecting CO2 or carbonated water in oil wells
Definitions
- the present invention relates to an enhanced oil recovery process that is integrated with a synthesis gas generation process, such as gasification or reforming, involving combined capture and recycle of carbon dioxide from both processes.
- a synthesis gas generation process such as gasification or reforming
- EOR enhanced oil recovery
- oil is produced using the natural pressure of an oil reservoir to drive the crude into the well bore from where it is brought to the surface with conventional pumps. After some period of production, the natural pressure of the oil reservoir decreases and production dwindles.
- producers incorporated secondary recovery by utilizing injected water, steam and/or natural gas to drive the crude to the well bore prior to pumping it to the surface.
- EOR enhanced oil recovery
- CO 2 from natural sources can be utilized, but generally requires the natural source to be in the proximity of the oil reservoir to avoid the construction and use of pipelines, which could make such use uneconomical.
- Synthesis gas production operations include, for example, catalytic gasification and hydromethanation processes, non-catalytic gasification processes and methane reforming processes. These processes typically produce one or more of methane, hydrogen and/or syngas (a mixture of hydrogen and carbon monoxide) as a raw gas product, which can be processed and ultimately used for power generation and/or other industrial applications. These processes also produce CO 2 , which is removed via acid gas removal processes, as is generally known to those of ordinary skill in the relevant art. Historically, this CO 2 has simply been vented to the atmosphere but, in view of environmental concerns, capture and sequestration/use of this CO 2 is becoming a necessity. EOR is thus a logical outlet for CO 2 streams from synthesis gas production operations.
- At least one such synthesis gas production operation which utilizes a CO 2 by-product stream for EOR currently exists at the Great Plains Synfuels Plant (near Beulah, North Dakota USA).
- coal/lignite is gasified to a synthesis gas stream containing carbon dioxide, which is separated via a solvent-based acid gas removal technique.
- the resulting CO 2 stream (which is greater than 95% pure) is compressed and transported via a 205-mile supercritical CO 2 pipeline to oil fields in Canada for use in EOR operations. This operation is described in more detail in Perry and Eliason, “CO 2 Recovery and Sequestration at Dakota Gasification Company” (October 2004), available on the Dakota Gasification Company website.
- a disadvantage in this operation is the pipeline, as supercritical CO 2 is considered a hazardous material.
- the construction, permitting, operation and maintenance of a supercritical CO 2 pipeline, particularly one as long as 205 miles, is expensive.
- a more advantageous way to get the CO 2 from the synthesis gas operation to the EOR site would, therefore, be highly desirable.
- the present invention provides an integrated process to (i) produce an acid gas-depleted gaseous hydrocarbon product steam, (ii) produce an acid gas-depleted synthesis gas stream, (iii) produce a liquid hydrocarbon product stream and (iv) enhance production of a hydrocarbon-containing fluid from an underground hydrocarbon reservoir, the process comprising the steps of:
- synthesis gas stream from a carbonaceous feedstock, the synthesis gas stream comprising (a) at least one of carbon monoxide and carbon dioxide, and (b) at least one of hydrogen and methane;
- the present invention provides a process to enhance production of a hydrocarbon-containing fluid from an underground hydrocarbon reservoir via a hydrocarbon production well, by injecting a pressurized carbon dioxide stream into an underground hydrocarbon reservoir, wherein the hydrocarbon-containing fluid comprises carbon dioxide, and wherein the pressurized carbon dioxide stream is generated by a process comprising the steps of:
- synthesis gas stream from a carbonaceous feedstock, the synthesis gas stream comprising (a) at least one of carbon monoxide and carbon dioxide, and (b) at least one of hydrogen and methane;
- the invention provides an apparatus for generating a liquid hydrocarbon product stream, an acid gas-depleted gaseous hydrocarbon product stream and an acid gas-depleted synthesis gas stream, the apparatus comprising:
- synthesis gas production system adapted to produce a synthesis gas from a carbonaceous feedstock, the synthesis gas comprising (i) at least one of carbon monoxide and carbon dioxide, and (ii) at least one of hydrogen and methane;
- a separation device in fluid communication with the hydrocarbon production well, the separation device adapted (i) to receive the hydrocarbon fluid from the hydrocarbon production well, and (ii) to separate the hydrocarbon fluid into the liquid hydrocarbon product stream and a gaseous hydrocarbon stream comprising carbon dioxide;
- a second acid gas absorber unit in fluid communication with the synthesis gas generation system, the second acid gas absorber unit adapted to (i) receive the synthesis gas from the synthesis gas generation system, and (ii) treat the synthesis gas to remove acid gases and produce the acid gas-depleted synthesis gas stream and a second acid gas-rich absorber stream;
- an absorber regeneration unit in fluid communication with the first acid gas absorber unit and the second acid gas absorber unit, the absorber regeneration unit adapted to (i) receive the first acid gas-rich absorber stream from the first acid gas absorber unit and the second acid gas-rich absorber stream from the second acid gas absorber unit, (ii) remove acid gases from the first acid gas-rich absorber stream and the second acid gas-rich absorber stream, and (iii) generate an acid gas-lean absorber stream and a carbon dioxide-rich recycle stream; and
- FIG. 1 is a diagram of an embodiment of an integrated process in accordance with the present invention.
- FIG. 2 is a diagram of an embodiment of the gas processing portion of the overall integrated process.
- the present disclosure relates to integrating synthesis gas production processes with enhanced oil recovery processes. Further details are provided below.
- pressures expressed in psi units are gauge, and pressures expressed in kPa units are absolute.
- the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
- a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus.
- “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
- substantially portion means that greater than about 90% of the referenced material, preferably greater than about 95% of the referenced material, and more preferably greater than about 97% of the referenced material.
- the percent is on a molar basis when reference is made to a molecule (such as methane, carbon dioxide, carbon monoxide and hydrogen sulfide), and otherwise is on a weight basis (such as the liquid component of the hydrocarbon-containing fluid).
- the term “predominant portion”, as used herein, unless otherwise defined herein, means that greater than about 50% of the referenced material. The percent is on a molar basis when reference is made to a molecule (such as hydrogen, methane, carbon dioxide, carbon monoxide and hydrogen sulfide), and otherwise is on a weight basis (such as the liquid component of the hydrocarbon-containing fluid).
- hydrocarbon-containing fluid means a fluid comprising any hydrocarbon liquid and/or gas.
- a hydrocarbon-containing fluid may also comprise solid particles. Oil, gas-condensate and the like, and also their mixtures with other liquids such as water, may be examples of a liquid contained in a hydrocarbon-containing fluid. Any gaseous hydrocarbon (for example, methane, ethane, propane, propylene, butane or the like), and mixtures of gaseous hydrocarbons, may be contained in a hydrocarbon-containing fluid.
- the hydrocarbon-containing fluid is recovered from an underground hydrocarbon reservoir, such as an oil-bearing formation, a gas-condensate reservoir, a natural gas reservoir and the like.
- carbonaceous as used herein is synonymous with hydrocarbon.
- carbonaceous material as used herein is a material containing organic hydrocarbon content. Carbonaceous materials can be classified as biomass or non-biomass materials as defined herein.
- biomass refers to carbonaceous materials derived from recently (for example, within the past 100 years) living organisms, including plant-based biomass and animal-based biomass.
- biomass does not include fossil-based carbonaceous materials, such as coal. For example, see US2009/0217575A1 and US2009/0217587A1.
- plant-based biomass means materials derived from green plants, crops, algae, and trees, such as, but not limited to, sweet sorghum, bagasse, sugarcane, bamboo, hybrid poplar, hybrid willow, albizia trees, eucalyptus, alfalfa, clover, oil palm, switchgrass, sudangrass, millet, jatropha, and miscanthus (e.g., Miscanthus ⁇ giganteus).
- Biomass further include wastes from agricultural cultivation, processing, and/or degradation such as corn cobs and husks, corn stover, straw, nut shells, vegetable oils, canola oil, rapeseed oil, biodiesels, tree bark, wood chips, sawdust, and yard wastes.
- animal-based biomass means wastes generated from animal cultivation and/or utilization.
- biomass includes, but is not limited to, wastes from livestock cultivation and processing such as animal manure, guano, poultry litter, animal fats, and municipal solid wastes (e.g., sewage).
- non-biomass means those carbonaceous materials which are not encompassed by the term “biomass” as defined herein.
- non-biomass include, but is not limited to, anthracite, bituminous coal, sub-bituminous coal, lignite, petroleum coke, asphaltenes, liquid petroleum residues or mixtures thereof.
- anthracite bituminous coal
- sub-bituminous coal lignite
- petroleum coke lignite
- asphaltenes liquid petroleum residues or mixtures thereof.
- petroleum coke and “petcoke” as used here include both (i) the solid thermal decomposition product of high-boiling hydrocarbon fractions obtained in petroleum processing (heavy residues—“resid petcoke”); and (ii) the solid thermal decomposition product of processing tar sands (bituminous sands or oil sands—“tar sands petcoke”).
- Such carbonization products include, for example, green, calcined, needle and fluidized bed petcoke.
- Resid petcoke can also be derived from a crude oil, for example, by coking processes used for upgrading heavy-gravity residual crude oil, which petcoke contains ash as a minor component, typically about 1.0 wt % or less, and more typically about 0.5 wt % of less, based on the weight of the coke.
- the ash in such lower-ash cokes comprises metals such as nickel and vanadium.
- Tar sands petcoke can be derived from an oil sand, for example, by coking processes used for upgrading oil sand.
- Tar sands petcoke contains ash as a minor component, typically in the range of about 2 wt % to about 12 wt %, and more typically in the range of about 4 wt % to about 12 wt %, based on the overall weight of the tar sands petcoke.
- the ash in such higher-ash cokes comprises materials such as silica and/or alumina.
- Petroleum coke has an inherently low moisture content, typically, in the range of from about 0.2 to about 2 wt % (based on total petroleum coke weight); it also typically has a very low water soaking capacity to allow for conventional catalyst impregnation methods.
- the resulting particulate compositions contain, for example, a lower average moisture content which increases the efficiency of downstream drying operation versus conventional drying operations.
- the petroleum coke can comprise at least about 70 wt % carbon, at least about 80 wt % carbon, or at least about 90 wt % carbon, based on the total weight of the petroleum coke.
- the petroleum coke comprises less than about 20 wt % inorganic compounds, based on the weight of the petroleum coke.
- asphalte as used herein is an aromatic carbonaceous solid at room temperature, and can be derived, for example, from the processing of crude oil and crude oil tar sands.
- coal as used herein means peat, lignite, sub-bituminous coal, bituminous coal, anthracite, or mixtures thereof.
- the coal has a carbon content of less than about 85%, or less than about 80%, or less than about 75%, or less than about 70%, or less than about 65%, or less than about 60%, or less than about 55%, or less than about 50% by weight, based on the total coal weight.
- the coal has a carbon content ranging up to about 85%, or up to about 80%, or up to about 75% by weight, based on the total coal weight.
- Examples of useful coal include, but are not limited to, Illinois #6, Pittsburgh #8, Beulah (ND), Utah Blind Canyon, and Powder River Basin (PRB) coals.
- Anthracite, bituminous coal, sub-bituminous coal, and lignite coal may contain about 10 wt %, from about 5 to about 7 wt %, from about 4 to about 8 wt %, and from about 9 to about 11 wt %, ash by total weight of the coal on a dry basis, respectively.
- the ash content of any particular coal source will depend on the rank and source of the coal, as is familiar to those skilled in the art. See, for example, “Coal Data: A Reference”, Energy Information Administration, Office of Coal, Nuclear, Electric and Alternate Fuels, U.S. Department of Energy, DOE/EIA-0064(93), February 1995.
- the ash produced from combustion of a coal typically comprises both a fly ash and a bottom ash, as are familiar to those skilled in the art.
- the fly ash from a bituminous coal can comprise from about 20 to about 60 wt % silica and from about 5 to about 35 wt % alumina, based on the total weight of the fly ash.
- the fly ash from a sub-bituminous coal can comprise from about 40 to about 60 wt % silica and from about 20 to about 30 wt % alumina, based on the total weight of the fly ash.
- the fly ash from a lignite coal can comprise from about 15 to about 45 wt % silica and from about 20 to about 25 wt % alumina, based on the total weight of the fly ash. See, for example, Meyers, et al. “Fly Ash. A Highway Construction Material,” Federal Highway Administration, Report No. FHWA-IP-76-16, Washington, D.C., 1976.
- the bottom ash from a bituminous coal can comprise from about 40 to about 60 wt % silica and from about 20 to about 30 wt % alumina, based on the total weight of the bottom ash.
- the bottom ash from a sub-bituminous coal can comprise from about 40 to about 50 wt % silica and from about 15 to about 25 wt % alumina, based on the total weight of the bottom ash.
- the bottom ash from a lignite coal can comprise from about 30 to about 80 wt % silica and from about 10 to about 20 wt % alumina, based on the total weight of the bottom ash. See, for example, Moulton, Lyle K. “Bottom Ash and Boiler Slag,” Proceedings of the Third International Ash Utilization Symposium, U.S. Bureau of Mines, Information Circular No. 8640, Washington, D.C., 1973.
- a carbonaceous material such as methane can be biomass or non-biomass under the above definitions depending on its source of origin.
- unit refers to a unit operation. When more than one “unit” is described as being present, those units are operated in a parallel fashion.
- an acid gas removal unit may comprise a hydrogen sulfide removal unit followed in series by a carbon dioxide removal unit.
- a contaminant removal unit may comprise a first removal unit for a first contaminant followed in series by a second removal unit for a second contaminant.
- a compressor may comprise a first compressor to compress a stream to a first pressure, followed in series by a second compressor to further compress the stream to a second (higher) pressure.
- an acid gas-depleted gaseous hydrocarbon product stream ( 31 ), an acid gas-depleted synthesis gas stream ( 30 ) and a liquid hydrocarbon product stream ( 85 ) are produced in an integrated EOR and synthesis gas production process as illustrated in FIGS. 1 and 2 .
- the EOR portion of the process involves injecting a pressurized carbon dioxide stream ( 89 ) via an injection well ( 500 ) (one or more) into an underground hydrocarbon reservoir ( 20 ) utilizing techniques well known to those of ordinary skill in the relevant art.
- the pressurized carbon dioxide stream ( 89 ) which will typically be in a supercritical fluid state, serves to enhance production of a hydrocarbon fluid ( 82 ) from a production well ( 600 ) through a combination of mechanisms typically involving a repressurization of the underground reservoir and a viscosity reduction of the trapped hydrocarbon (improving flow properties).
- the pressurized carbon dioxide stream ( 89 ) will be injected into the underground reservoir at a pressure of at least about 1200 psig (about 8375 kPa), or at least about 1500 psig (about 10444 kPa), or at least about 2000 psig (about 13891 kPa).
- carbon dioxide-based EOR can also involve co-injection of pressurized water, steam, nitrogen and other fluids, or alternating injections of a pressurized carbon dioxide-rich stream, a water/steam stream and/or a nitrogen stream.
- the actual carbon dioxide-based EOR process utilized is not critical to the present invention in its broadest sense.
- the resulting hydrocarbon-containing fluid ( 82 ) is produced and recovered through a hydrocarbon production well ( 600 ) (one or more).
- the produced hydrocarbon-containing fluid ( 82 ) will typically contain liquid and gas hydrocarbon components, as well as other liquid and gaseous components depending on the hydrocarbon reservoir and EOR conditions.
- the liquid hydrocarbon component can generally be considered as a crude oil, while the gaseous hydrocarbon component will typically comprise hydrocarbons that are gases at ambient conditions, such as methane, ethane, propane, propylene and butane (typical components of natural gas). Other typical liquid components include water or brine.
- the hydrocarbon-containing fluid ( 82 ) will also comprise carbon dioxide, and may comprise other gaseous components such as hydrogen sulfide (from a sour well) and nitrogen.
- the hydrocarbon-containing fluid ( 82 ) may also include solid carbon and mineral matter.
- the produced hydrocarbon-containing fluid ( 82 ) is passed to a separation device ( 300 ) to separate the gaseous components from the liquid/solid components to generate a gaseous hydrocarbon stream ( 84 ), a liquid hydrocarbon product stream ( 85 ) and, optionally, a stream ( 86 ) containing solids components from the hydrocarbon-containing fluid ( 82 ).
- the solids may also optionally be carried with the liquid hydrocarbon product stream ( 85 ) for later separation, or separated out prior to separation device ( 300 ), by well-known techniques such as settling, centrifugation and/or filtration.
- larger/denser solids are separated in conjunction with separation device ( 300 ), and finer solids that may become entrained in liquid hydrocarbon product stream ( 85 ) are separated subsequently through well-known techniques such as filtration.
- Suitable separation devices for use as separation device ( 300 ) are well known to those of ordinary skill in the art and include, for example, single and multistage horizontal separators and cyclones.
- the actual separation device utilized is not critical to the present invention in its broadest sense.
- the liquid hydrocarbon product stream ( 85 ) can subsequently be processed to separate out the water and other contaminants, then further processed (e.g., refined) to a variety of end products or for a variety of end uses, as is well-known to those or ordinary skill in the relevant art.
- a stream ( 86 ) containing solids components that will typically be removed from separation device ( 300 ) as a concentrated slurry or with some portion of the liquid content of the hydrocarbon-containing fluid ( 82 ). Oil that may be withdrawn with the solids in stream ( 86 ) can be recovered from the solids via washing or other techniques well-known to those of ordinary skill in the relevant art.
- the resulting gaseous hydrocarbon stream ( 84 ) exiting separation device ( 300 ) typically comprises at least a substantial portion (or substantially all) of the gaseous components from the hydrocarbon-containing fluid ( 82 ), including at least a substantial portion (or substantially all) of the gaseous hydrocarbons and carbon dioxide from the hydrocarbon-containing fluid ( 82 ).
- the gaseous hydrocarbon stream ( 84 ) may also comprise minor amounts of water vapor, which should be substantially removed prior to treatment in the first acid gas absorber unit ( 230 ) as discussed below, as well as minor amount of other contaminants such as hydrogen sulfide.
- gaseous hydrocarbon stream ( 84 ) exiting separation device ( 300 ) is ultimately processed with synthesis gas stream ( 50 ) in an acid gas removal unit as discussed below.
- gaseous hydrocarbon stream ( 84 ) Prior to processing in the acid gas removal unit, gaseous hydrocarbon stream ( 84 ) may optionally be compressed or heated (not depicted) to temperature and pressure conditions suitable for optional downstream processing as further described below.
- Synthesis gas stream ( 50 ) contains (i) at least one of carbon monoxide and carbon dioxide, and (ii) at least one of hydrogen and methane.
- the actual composition of synthesis gas stream ( 50 ) will depend on the synthesis gas process and carbonaceous feedstock utilized to generate the stream, including any gas processing that may occur before acid gas removal.
- synthesis gas stream ( 50 ) comprises carbon dioxide and hydrogen. In another embodiment, synthesis gas stream ( 50 ) comprises carbon dioxide and methane. In another embodiment, synthesis gas stream ( 50 ) comprises carbon dioxide, methane and hydrogen. In another embodiment, synthesis gas stream ( 50 ) comprises carbon monoxide and hydrogen. In another embodiment, synthesis gas stream ( 50 ) comprises carbon monoxide, methane and hydrogen. In another embodiment, synthesis gas stream ( 50 ) comprises carbon dioxide, carbon monoxide, methane and hydrogen. The synthesis gas stream ( 50 ) may also contain other gaseous components such as, for example, hydrogen sulfide, steam and other gaseous hydrocarbons again depending on the synthesis gas production process and carbonaceous feedstock.
- gaseous components such as, for example, hydrogen sulfide, steam and other gaseous hydrocarbons again depending on the synthesis gas production process and carbonaceous feedstock.
- Any synthesis gas generating process can be utilized in the context of the present invention, so long as the synthesis gas generating process (including gas processing prior to acid gas removal) results in a synthesis gas stream as required in the context of the present invention.
- Suitable synthesis gas processes are generally known to those of ordinary skill in the relevant art, and many applicable technologies are commercially available.
- Non-limiting examples of different types of suitable synthesis gas generation processes are discussed below. These may be used individually or in combination. All synthesis gas generation process will involve a reactor, which is generically depicted as ( 110 ) in FIG. 2 , where a carbonaceous feedstock ( 10 ) will be processed to produce synthesis gases, which may be further treated prior to acid gas removal. General reference can be made to FIG. 2 in the context of the various synthesis gas generating processes described below.
- the synthesis gas generating process is based on a gas-fed methane partial oxidation/reforming process, such as non-catalytic gaseous partial oxidation, catalytic autothermal reforming or catalytic stream-methane reforming process.
- a gas-fed methane partial oxidation/reforming process such as non-catalytic gaseous partial oxidation, catalytic autothermal reforming or catalytic stream-methane reforming process.
- the methane-containing stream useful in these processes comprises methane in a predominant amount, and may comprise other gaseous hydrocarbon and components.
- Examples of commonly used methane-containing streams include natural gas and synthetic natural gas.
- an oxygen-rich gas stream ( 12 ) is fed into the reactor ( 110 ) along with carbonaceous feedstock ( 10 ).
- steam ( 14 ) may also be fed into the reactor ( 110 ).
- steam ( 14 ) is fed into the reactor along with the carbonaceous feedstock ( 10 ).
- minor amounts of other gases such as carbon dioxide, hydrogen and/or nitrogen may also be fed in the reactor ( 110 ).
- Reaction and other operating conditions, and equipment and configurations, of the various reactors and technologies are in a general sense known to those of ordinary skill in the relevant art, and are not critical to the present invention in its broadest sense.
- the synthesis gas generating process is based on a non-catalytic thermal gasification process, such as a partial oxidation gasification process (like an oxygen-blown gasifier), where a non-gaseous (liquid, semi-solid and/or solid) hydrocarbon is utilized as the carbonaceous feedstock ( 10 ).
- a non-catalytic thermal gasification process such as a partial oxidation gasification process (like an oxygen-blown gasifier)
- a non-gaseous (liquid, semi-solid and/or solid) hydrocarbon is utilized as the carbonaceous feedstock ( 10 ).
- a non-catalytic thermal gasification process such as a partial oxidation gasification process (like an oxygen-blown gasifier)
- a non-gaseous (liquid, semi-solid and/or solid) hydrocarbon is utilized as the carbonaceous feedstock ( 10 ).
- Oxygen-blown solids/liquids gasifiers potentially suitable for use in conjunction with the present invention are, in a general sense, known to those of ordinary skill in the relevant art and include, for example, those based on technologies available from Royal Dutch Shell plc, ConocoPhillips Company, Siemens AG, Lurgi AG (Sasol), General Electric Company and others.
- Other potentially suitable syngas generators are disclosed, for example, in US2009/0018222A1, US2007/0205092A1 and U.S. Pat. No. 6,863,878.
- an oxygen-rich gas stream ( 12 ) is fed into the reactor ( 110 ) along with the carbonaceous feedstock ( 10 ).
- steam ( 14 ) may also be fed into the reactor ( 110 ), as well as other gases such as carbon dioxide, hydrogen, methane and/or nitrogen.
- steam ( 14 ) may be utilized as an oxidant at elevated temperatures in place of all or a part of the oxygen-rich gas stream ( 12 ).
- the gasification in the reactor ( 110 ) will typically occur in a fluidized bed of the carbonaceous feedstock ( 10 ) that is fluidized by the flow of the oxygen-rich gas stream ( 12 ), steam ( 14 ) and/or other fluidizing gases (like carbon dioxide and/or nitrogen) that may be fed to reactor ( 110 ).
- thermal gasification is a non-catalytic process, so no gasification catalyst needs to be added to the carbonaceous feedstock ( 10 ) or into the reactor ( 110 ); however, a catalyst that promotes syngas formation may be utilized.
- thermal gasification processes are typically operated under high temperature and pressure conditions, and may run under slagging or non-slagging operating conditions depending on the process and carbonaceous feedstock.
- Reaction and other operating conditions, and equipment and configurations, of the various reactors and technologies are in a general sense known to those of ordinary skill in the relevant art, and are not critical to the present invention in its broadest sense.
- the synthesis gas generating process is a catalytic gasification/hydromethanation process, in which gasification of a non-gaseous carbonaceous feedstock ( 10 ) takes place in a reactor ( 110 ) in the presence of steam and a catalyst to result in a methane-enriched gas stream as the synthesis gas stream ( 50 ), which typically comprises methane, hydrogen, carbon monoxide, carbon dioxide and steam.
- the overall reaction is essentially thermally balanced; however, due to process heat losses and other energy requirements (such as required for evaporation of moisture entering the reactor with the feedstock), some heat must be added to maintain the thermal balance.
- the reactions are also essentially syngas (hydrogen and carbon monoxide) balanced (syngas is produced and consumed); therefore, as carbon monoxide and hydrogen are withdrawn with the product gases, carbon monoxide and hydrogen need to be added to the reaction as required to avoid a deficiency.
- a superheated gas stream of steam ( 14 ) and syngas ( 16 ) (carbon monoxide and hydrogen) is often fed to the reactor ( 110 ).
- the carbon monoxide and hydrogen streams are recycle streams separated from the product gas, and/or are provided by reforming a portion of the product methane.
- the carbonaceous feedstocks useful in these processes include, for example, a wide variety of biomass and non-biomass materials.
- Catalysts utilized in these processes include, for example, alkali metals, alkaline earth metals and transition metals, and compounds, mixtures and complexes thereof.
- the temperature and pressure operating conditions in a catalytic gasification/hydromethanation process are typically milder (lower temperature and pressure) than a non-catalytic gasification process, which can sometimes have advantages in terms of cost and efficiency.
- All of the above described synthesis gas generation processes typically will generate a synthesis gas stream ( 50 ) of a temperature higher than suitable for feeding downstream gas processes (including second acid gas absorber unit ( 210 )), so upon exit from reactor ( 110 ) the synthesis gas stream ( 50 ) is typically passed through a heat exchanger unit ( 140 ) to remove heat energy and generate a cooled synthesis gas stream ( 52 ).
- the heat energy recovered in heat exchanger unit ( 140 ) can be used, for example, to generate steam and/or superheat various process streams, as will be recognized by a person of ordinary skill in the art. Any steam generated can be used for internal process requirements and/or used to generate electrical power.
- the resulting cooled synthesis gas stream ( 52 ) will typically exit heat exchanger unit ( 140 ) at a temperature ranging from about 450° F. (about 232° C.) to about 1100° F. (about 593° C.), more typically from about 550° F. (about 288° C.) to about 950° F. (about 510° C.), and at a pressure suitable for subsequent acid gas removal processing (taking into account any intermediate processing). Typically, this pressure will be from about 50 psig (about 446 kPa) to about 800 psig (about 5617 kPa), more typically from about 400 psig (about 2860 kPa) to about 600 psig (about 4238 kPa).
- Synthesis gas stream ( 50 ) and gaseous hydrocarbon stream ( 84 ) may be processed in various treatment processes, which will be primarily dependent on the composition, temperature and pressure of the two streams, and any desired end products.
- Processing options prior to acid gas removal typically include, for example, one or more of sour shift ( 700 ) (water gas shift), contaminant removal ( 710 ) and dehydration ( 720 and 720 a ). While these intermediate processing steps can occur in any order, dehydration ( 720 and 720 a ) will usually occur just prior to acid gas removal (last in the series), as a substantial portion of any water in synthesis gas stream ( 50 ) and gaseous hydrocarbon stream ( 84 ) desirably should be removed prior to treatment in acid gas absorber units ( 210 and 230 ).
- the gaseous hydrocarbon stream ( 84 ) will require at least some compression prior to treatment in first acid gas absorber unit ( 230 ).
- all or a part of such stream can be supplied to a sour shift reactor ( 700 ).
- sour shift reactor ( 700 ) the gases undergo a sour shift reaction (also known as a water-gas shift reaction) in the presence of an aqueous medium (such as steam) to convert at least a predominant portion (or a substantial portion, or substantially all) of the CO to CO 2 , which also increases the fraction of H 2 in order to produce a hydrogen-enriched stream ( 54 ).
- a sour shift reaction also known as a water-gas shift reaction
- an aqueous medium such as steam
- a sour shift process is described in detail, for example, in U.S. Pat. No. 7,074,373.
- the process involves adding water, or using water contained in the gas, and reacting the resulting water-gas mixture adiabatically over a steam reforming catalyst.
- Typical steam reforming catalysts include one or more Group VIII metals on a heat-resistant support.
- Suitable reaction conditions and suitable reactors can vary depending on the amount of CO that must be depleted from the gas stream.
- the sour gas shift can be performed in a single stage within a temperature range from about 100° C., or from about 150° C., or from about 200° C., to about 250° C., or to about 300° C., or to about 350° C.
- the shift reaction can be catalyzed by any suitable catalyst known to those of skill in the art.
- Such catalysts include, but are not limited to, Fe 2 O 3 -based catalysts, such as Fe 2 O 3 —Cr 2 O 3 catalysts, and other transition metal-based and transition metal oxide-based catalysts.
- the sour gas shift can be performed in multiple stages. In one particular embodiment, the sour gas shift is performed in two stages. This two-stage process uses a high-temperature sequence followed by a low-temperature sequence. The gas temperature for the high-temperature shift reaction ranges from about 350° C. to about 1050° C. Typical high-temperature catalysts include, but are not limited to, iron oxide optionally combined with lesser amounts of chromium oxide. The gas temperature for the low-temperature shift ranges from about 150° C.
- Low-temperature shift catalysts include, but are not limited to, copper oxides that may be supported on zinc oxide or alumina. Suitable methods for the sour shift process are described in previously incorporated US2009/0246120A1.
- the sour shift reaction is exothermic, so it is often carried out with a heat exchanger (not depicted) to permit the efficient use of heat energy.
- Shift reactors employing these features are well known to those of skill in the art. Recovered heat energy can be used, for example, to generate steam, superheat various process streams and/or preheat boiler feed water for use in other steam generating operations.
- An example of a suitable shift reactor is illustrated in previously incorporated U.S. Pat. No. 7,074,373, although other designs known to those of skill in the art are also effective.
- a portion of the stream can be split off to bypass sour shift reactor ( 700 ) and be combined with hydrogen-enriched stream ( 54 ) at some point prior to second acid gas absorber unit ( 210 ). This is particularly useful when it is desired to recover a separate methane by-product, as the retained carbon monoxide can be subsequently methanated as discussed below.
- the contamination levels of synthesis gas stream ( 50 ) will depend on the nature of the carbonaceous feedstock and the synthesis gas generation conditions. For example, petcoke and certain coals can have high sulfur contents, leading to higher sulfur oxide (SOx), H 2 S and/or COS contamination. Certain coals can contain significant levels of mercury which can be volatilized during the synthesis gas generation. Other feedstocks can be high in nitrogen content, leading to ammonia, nitrogen oxides (NOx) and/or cyanides.
- second acid gas absorber unit ( 210 ) Some of these contaminants are typically removed in second acid gas absorber unit ( 210 ), such as H 2 S and COS. Others such as ammonia and mercury, require removal prior to second acid gas absorber unit ( 210 ).
- contaminant removal of a particular contaminant should remove at least a substantial portion (or substantially all) of that contaminant from the so-treated cleaned gas stream ( 56 ), typically to levels at or lower than the specification limits for the desired second acid gas absorber unit ( 210 ), or the desired end product.
- gaseous hydrocarbon stream ( 84 ) may be treated separately for contaminant removal as needed.
- Contaminant removal process are in a general sense well know to those of ordinary skill in the relevant art, as exemplified in many of the previously-incorporated references.
- the synthesis gas stream ( 50 ) and gaseous hydrocarbon stream ( 84 ) should be treated to reduced residual water content via a dehydration unit ( 720 ) and ( 720 a ) to produce a dehydrated stream ( 58 ) and ( 58 a ) for feeding to second acid gas absorber unit ( 210 ) and first acid gas absorber unit ( 230 ), respectively.
- Suitable dehydration units include a knock-out drum or similar water separation device, and/or water absorption processes such as glycol treatment.
- the synthesis gas stream ( 50 ) and the gaseous hydrocarbon stream ( 84 ) are processed in an acid gas removal unit to remove carbon dioxide and other acid gases (such as hydrogen sulfide if present), and generate a carbon dioxide-rich recycle stream ( 87 ), an acid gas-depleted gaseous hydrocarbon product stream ( 31 ) and an acid gas-depleted synthesis gas stream ( 30 ).
- the synthesis gas stream ( 50 ) and the gaseous hydrocarbon stream ( 84 ) are first individually treated in a second acid gas absorber unit ( 210 ) and a first acid gas absorber unit ( 230 ), respectively, to generate a separate acid gas-depleted synthesis gas stream ( 30 ) and second acid gas-rich absorber stream ( 35 ), and a separate acid gas-depleted gaseous hydrocarbon product stream ( 31 ) and first acid gas-rich absorber stream ( 36 ).
- the resulting acid gas-depleted gaseous hydrocarbon product stream ( 31 ) and an acid gas-depleted synthesis gas stream ( 30 ) may be co-processed or separately processed as described further below.
- first acid gas-rich absorber stream ( 36 ) and second acid gas-rich absorber stream ( 35 ) are co-processed in an absorber regeneration unit ( 250 ) to ultimately result in an acid gas stream containing the combined acid gases (and other contaminants) removed from both synthesis gas stream ( 50 ) and gaseous hydrocarbon stream ( 84 ).
- First acid gas-rich absorber stream ( 36 ) and second acid gas-rich absorber stream ( 35 ) may be combined prior to or within absorber regeneration unit ( 250 ) for co-processing.
- a carbon dioxide-rich recycle stream ( 87 ) is generated containing a substantial portion of carbon dioxide from both synthesis gas stream ( 50 ) and gaseous hydrocarbon stream ( 84 ).
- An acid gas-lean absorber stream ( 70 ) is also generated, which can be recycled back to one or both of first acid gas absorber unit ( 230 ) and second acid gas absorber unit ( 210 ) along with make-up absorber as required. If one or both of synthesis gas stream ( 50 ) and gaseous hydrocarbon stream ( 84 ) contain other acid gas contaminants, such as hydrogen sulfide, then an additional stream may be generated, such as hydrogen sulfide stream ( 88 ).
- Acid gas removal processes typically involve contacting a gas stream with a solvent such as monoethanolamine, diethanolamine, methyldiethanolamine, diisopropylamine, diglycolamine, a solution of sodium salts of amino acids, methanol, hot potassium carbonate or the like to generate CO 2 and/or H 2 S laden absorbers.
- a solvent such as monoethanolamine, diethanolamine, methyldiethanolamine, diisopropylamine, diglycolamine, a solution of sodium salts of amino acids, methanol, hot potassium carbonate or the like to generate CO 2 and/or H 2 S laden absorbers.
- a solvent such as monoethanolamine, diethanolamine, methyldiethanolamine, diisopropylamine, diglycolamine, a solution of sodium salts of amino acids, methanol, hot potassium carbonate or the like.
- One method can involve the use of Selexol® (UOP LLC, Des Plaines, Ill. USA) or Rectisol® (Lurgi AG, Frankfurt
- At least a substantial portion (e.g., substantially all) of the CO 2 and/or H 2 S (and other remaining trace contaminants) should be removed via the acid gas removal processes.
- “Substantial” removal in the context of acid gas removal means removal of a high enough percentage of the component such that a desired end product can be generated. The actual amounts of removal may thus vary from component to component. Desirably, only trace amounts (at most) of H 2 S should be present in the acid gas-depleted gaseous hydrocarbon product stream, although higher amounts of CO 2 may be tolerable depending on the desired end product.
- At least about 85%, or at least about 90%, or at least about 92%, of the CO 2 , and at least about 95%, or at least about 98%, or at least about 99.5%, of the H 2 S, should be removed, based on the amount of those components contained in the streams fed to the acid gas removal.
- Any recovered H 2 S ( 88 ) from the acid gas removal can be converted to elemental sulfur by any method known to those skilled in the art, including the Claus process. Sulfur can be recovered as a molten liquid.
- the recovered carbon dioxide-rich recycle stream ( 87 ) is in whole or in part compressed via compressor ( 400 ) to generate pressurized carbon dioxide stream ( 89 ) for the EOR portion of the process.
- a CO 2 product stream ( 90 ) can also optionally be split off of carbon dioxide-rich recycle stream ( 87 ) and/or pressurized carbon dioxide stream ( 89 ).
- Suitable compressors for compressing carbon dioxide-rich recycle stream ( 87 ) to appropriate pressures and conditions for EOR are in a general sense well-known to those of ordinary skill in the relevant art.
- the resulting acid gas-depleted gaseous hydrocarbon product stream ( 31 ) will generally comprise CH 4 and other gaseous hydrocarbons from the gaseous hydrocarbon stream ( 84 ), and typically no more than contaminant amounts of CO 2 , H 2 O, H 2 S and other contaminants.
- the resulting acid gas-depleted synthesis gas stream ( 30 ) will generally comprise one or both of CH 4 and H 2 , and optionally CO (for the downstream methanation), and typically no more than contaminant amounts of CO 2 , H 2 O, H 2 S and other contaminants.
- All or a portion of these two streams individually, or combined in whole or in part, may be processed to end products or for end uses as are well known to those of ordinary skill in the relevant art.
- the two streams may be combined at various points subsequent to acid gas removal.
- Non-limiting options are discussed below in reference to FIG. 2 .
- FIG. 2 only depicts some of the options as applied to acid gas-depleted synthesis gas stream ( 30 ), these options (and others) may be applied to gas-depleted gaseous hydrocarbon product stream ( 31 ) (or a combined stream) where appropriate.
- hydrogen may be separated from all or a portion of acid gas-depleted synthesis gas stream ( 30 ) (and/or the acid gas-depleted gaseous hydrocarbon product stream ( 31 )) according to methods known to those skilled in the art, such as cryogenic distillation, the use of molecular sieves, gas separation (e.g., ceramic or polymeric) membranes, and/or pressure swing adsorption (PSA) techniques.
- cryogenic distillation such as cryogenic distillation, the use of molecular sieves, gas separation (e.g., ceramic or polymeric) membranes, and/or pressure swing adsorption (PSA) techniques.
- gas separation e.g., ceramic or polymeric membranes
- PSA pressure swing adsorption
- a PSA device is utilized for hydrogen separation.
- PSA technology for separation of hydrogen from gas mixtures containing methane (and optionally carbon monoxide) is in general well-known to those of ordinary skill in the relevant art as disclosed, for example, in U.S. Pat. No. 6,379,645 (and other citations referenced therein).
- PSA devices are generally commercially available, for example, based on technologies available from Air Products and Chemicals Inc. (Allentown, Pa.), UOP LLC (Des Plaines, Ill.) and others.
- a hydrogen membrane separator can be used followed by a PSA device.
- Such separation provides a high-purity hydrogen product stream ( 72 ) and a hydrogen-depleted gas stream ( 74 ).
- the recovered hydrogen product stream ( 72 ) preferably has a purity of at least about 99 mole %, or at least 99.5 mole %, or at least about 99.9 mole %.
- the recovered hydrogen can be used, for example, as an energy source and/or as a reactant.
- the hydrogen can be used as an energy source for hydrogen-based fuel cells, or for power and/or steam generation ( 760 ).
- the hydrogen can also be used as a reactant in various hydrogenation processes, such as found in the chemical and petroleum refining industries.
- the hydrogen-depleted gas stream ( 74 ) will substantially comprise light hydrocarbons, such as methane (and generally predominantly methane, or substantially methane), with optional minor amounts of carbon monoxide (depending primarily on the extent of the sour shift reaction and bypass), carbon dioxide (depending primarily on the effectiveness of the acid gas removal process) and hydrogen (depending primarily on the extent and effectiveness of the hydrogen separation technology), and can be further processed/utilized as described below.
- light hydrocarbons such as methane (and generally predominantly methane, or substantially methane
- carbon monoxide depending primarily on the extent of the sour shift reaction and bypass
- carbon dioxide depending primarily on the effectiveness of the acid gas removal process
- hydrogen depending primarily on the extent and effectiveness of the hydrogen separation technology
- the acid gas-depleted synthesis gas stream ( 30 ) (and/or the acid gas-depleted gaseous hydrocarbon product stream ( 31 ), and/or the hydrogen-depleted sweetened gas stream ( 74 )) contains carbon monoxide and hydrogen, all or part of the stream may be fed to a (trim) methanation unit ( 740 ) to generate additional methane from the carbon monoxide and hydrogen, resulting in a methane-enriched gas stream ( 75 ).
- the methanation reaction can be carried out in any suitable reactor, e.g., a single-stage methanation reactor, a series of single-stage methanation reactors or a multistage reactor.
- Methanation reactors include, without limitation, fixed bed, moving bed or fluidized bed reactors. See, for instance, U.S. Pat. No. 3,958,957, U.S. Pat. No. 4,252,771, U.S. Pat. No. 3,996,014 and U.S. Pat. No. 4,235,044.
- Methanation reactors and catalysts are generally commercially available.
- the catalyst used in the methanation, and methanation conditions are generally known to those of ordinary skill in the relevant art, and will depend, for example, on the temperature, pressure, flow rate and composition of the incoming gas stream.
- the methane-enriched gas stream ( 75 ) may be, for example, further provided to a heat exchanger unit ( 750 ). While the heat exchanger unit ( 750 ) is depicted as a separate unit, it can exist as such and/or be integrated into methanation unit ( 740 ), thus being capable of cooling the methanation unit ( 740 ) and removing at least a portion of the heat energy from the methane-enriched stream ( 75 ) to reduce the temperature and generate a cooled methane-enriched stream ( 76 ).
- the recovered heat energy can be utilized, for example, to generate a process steam stream from a water and/or steam source.
- methane-enriched stream ( 75 ) can be recovered as a methane product stream ( 77 ) or, it can be further processed, when necessary, to separate and recover CH 4 by any suitable gas separation method known to those skilled in the art including, but not limited to, cryogenic distillation and the use of molecular sieves or gas separation (e.g., ceramic) membranes.
- gas separation method known to those skilled in the art including, but not limited to, cryogenic distillation and the use of molecular sieves or gas separation (e.g., ceramic) membranes.
- the acid gas-depleted synthesis gas stream ( 30 ), the acid gas-depleted hydrocarbon stream ( 31 ), the hydrogen-depleted gas stream ( 74 ), the methane-enriched gas stream ( 75 ), and/or a combination of the above is a “pipeline-quality natural gas”.
- a “pipeline-quality natural gas” typically refers to a methane-containing gas that is (1) within ⁇ 5% of the heating value of pure methane (whose heating value is 1010 btu/ft 3 under standard atmospheric conditions), (2) substantially free of water (typically a dew point of about ⁇ 40° C. or less), and (3) substantially free of toxic or corrosive contaminants.
- All or a portion of the acid gas-depleted synthesis gas stream ( 30 ) and/or acid gas-depleted gaseous hydrocarbon product stream ( 31 ) (or derivative product stream as discussed above) can, for example, be utilized for combustion and/or steam generation in a power generation block ( 760 ), for example, to produce electrical power ( 79 ) which may be either utilized within the plant or can be sold onto the power grid.
- All or a portion of these streams can also be used as a recycle hydrocarbon stream ( 78 ), for example, for use as carbonaceous feedstock ( 10 ) in a gaseous partial oxidation/methane reforming process, or for the generation of syngas feed stream ( 16 ) for use in a hydromethanation process (in, for example, a gaseous partial oxidation/methane reforming process). Both of these uses can, for example, ultimately result in an optimized production of hydrogen product stream ( 72 ), and carbon dioxide-rich recycle stream ( 87 ).
- the synthesis gas stream is produced by a catalytic steam methane reforming process utilizing a methane-containing stream as the carbonaceous feedstock.
- the synthesis gas stream is produced by a non-catalytic (thermal) gaseous partial oxidation process utilizing a methane-containing stream as the carbonaceous feedstock.
- the synthesis gas stream is produced by a catalytic autothermal reforming process utilizing a methane-containing stream as the carbonaceous feedstock.
- the methane-containing stream for use in these processes may be a natural gas stream, a synthetic natural gas stream or a combination thereof.
- the methane-containing stream comprises all or a portion of the acid gas-depleted gaseous hydrocarbon product stream, the acid gas-depleted synthesis gas stream, a combination of these streams, and/or a derivative of one or both of these streams after downstream processing.
- the resulting synthesis gas stream from these processes will typically comprise at least hydrogen and one or both of carbon monoxide and carbon dioxide, depending on gas processing prior to acid gas removal.
- the synthesis gas stream is produced by a non-catalytic thermal gasification process utilizing a non-gaseous carbonaceous material as the carbonaceous feedstock, such as coal, petcoke, biomass and mixtures thereof.
- a non-gaseous carbonaceous material such as coal, petcoke, biomass and mixtures thereof.
- the resulting synthesis gas stream from this process will typically comprise at least hydrogen and one or both of carbon monoxide and carbon dioxide, depending on gas processing prior to acid gas removal.
- the synthesis gas stream is produced by a catalytic hydromethanation process utilizing a non-gaseous carbonaceous material as the carbonaceous feedstock, such as coal, petcoke, biomass and mixtures thereof.
- a non-gaseous carbonaceous material such as coal, petcoke, biomass and mixtures thereof.
- the resulting synthesis gas stream from this process will typically comprise at least methane, hydrogen and carbon dioxide, and optionally carbon monoxide, depending on gas processing prior to acid gas removal.
- At least a portion of the synthesis gas stream is subject to a sour shift to generate a hydrogen-enriched stream.
- the hydrogen-enriched stream is subsequently treated in the acid gas removal step.
- the acid-gas depleted synthesis gas stream comprises hydrogen, and at least a portion of the hydrogen is separated to generate a hydrogen product stream and a hydrogen-depleted gas stream.
- this hydrogen-depleted gas stream is a pipeline-quality natural gas.
- the acid gas-depleted gaseous hydrocarbon product stream is a pipeline-quality natural gas.
- the acid-gas depleted synthesis gas stream comprises hydrogen and carbon monoxide, and is subject to a methanation to produce a methane-enriched gas stream, which can be a pipeline-quality natural gas.
- this hydrogen-depleted gas stream comprises hydrogen and carbon monoxide, and is subject to a methanation to produce a methane-enriched gas stream, which can be a pipeline-quality natural gas.
- At least a portion of the acid-gas depleted gaseous hydrocarbon product stream and/or the acid gas-depleted synthesis gas stream (or the hydrogen-depleted stream if present, or the methane-enriched stream if present), is the carbonaceous feedstock.
- At least a portion of the acid-gas depleted gaseous hydrocarbon product stream and/or acid gas-depleted synthesis gas stream is used to generate electrical power.
- At least a portion of the acid-gas depleted gaseous hydrocarbon product stream and/or acid gas-depleted synthesis gas stream is used to generate a syngas feed stream for use in a hydromethanation process.
- the synthesis gas stream and the gaseous hydrocarbon stream are subject to a dehydration prior to acid gas removal.
- the acid-gas lean absorber stream is recycled back to one or both of the first and second acid gas absorber units.
- the absorber regeneration unit is further adapted to (iv) provide the acid gas-lean absorber stream to one or both the first and second acid gas absorber units.
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Abstract
Description
Steam carbon: C+H2O→CO+H2 (I)
Water-gas shift: CO+H2O→H2+CO2 (II)
CO Methanation: CO+3H2→CH4+H2O (III)
Hydro-gasification: 2H2+C→CH4 (IV)
2C+2H2O→CH4+CO2 (V).
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